Fluorinated methyl ethers

ABSTRACT

A process is disclosed for producing a fluorinated ether of the formula R 2  CHOCF 2  A, where A is Cl or F, and each R is H, (CF 2 ) n  Cl, (CF 2 ) n  F or (CF 2 ) n  H (n is an integer from 1 to 10) by reacting a first reactant of the formula R 2  CHOY where Y is H, COF, COCl or COOCHR 2  (R is as defined above), a second reactant selected of the formula CZ 2  Cl 2  or COZ 2  where each Z is independently Cl or F (provided that when A is Cl, the second reactant is CZ 2  Cl 2 ), and HF; and recovering the fluorinated ether from the reaction products. Also disclosed are bis-ethers of the formula (CF 3  (CF 2 ) m ) 2  CHOCF 2  OCH (CF 2 ) m  CF 3 ) 2 , where m is an integer of 0 to 3, which can also be produced by the process.

This is a division of application Ser. No. 08/085,843, filed Jun. 30, 1993, now U.S. Pat. No. 5,382,704.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to ethers containing fluorine substituents, and more particularly to fluorinated methyl ethers and processes for their production.

2. Background

Chlorofluorocarbons (i.e., compounds containing only carbon, fluorine, and chlorine) have been used for many years as refrigerants, heat transfer media, foam expansion agents, aerosol propellants, solvents and power cycle working fluids. However, there has been recent concern that chlorofluorocarbons might be detrimental to the Earth's ozone layer. Consequently, there is a worldwide effort to find alternative compounds which contain fewer chlorine substituents. Fluorinated dimethylethers have been proposed as replacements for some CFCs (see e.g., U.S. Pat. No. 5,196,600). Other fluorinated ether compounds are under consideration for various applications. There is thus an interest in fluorinated ether compounds and a need for efficient processes for their production.

SUMMARY OF THE INVENTION

This invention provides a process for the manufacture of fluorinated ethers of the formula R₂ CHOCF₂ A wherein each R independently is selected from the group consisting of H, (CF₂)_(n) Cl, (CF₂)_(n) F and (CF₂)_(n) H, where n is an integer from 1 to 10 and wherein A is selected from the group consisting of Cl and F. The process comprises the step of reacting a first reactant of the formula R₂ CHOY, wherein Y is selected from the group consisting of H, COF, COCl and COOCHR₂, and each R is as defined above, a second reactant selected from the group consisting of CCl₄, CCl₃ F, CCl₂ F₂, COCl₂, COClF and COF₂ (provided that when A is Cl, the second reactant is selected from the group consisting of CCl₄, CCl₃ F, and CCl₂ F₂) and HF, and recovering the fluorinated ether from the reaction products. This invention further provides bis-ether compounds of the formula (CF₃ (CF₂)_(m))₂ CHOCF₂ OCH((CF₂)_(m) CF₃)₂, where m is an integer from 0 to 3.

DETAILS OF THE INVENTION

This invention involves reacting a first reactant of the formula R₂ CHOY, a second reactant of the formula CZ₂ Cl₂ or COZ₂ (where each Z is independently selected from Cl and F) and HF to produce a fluorinated methyl ether. Preferably, at least one R group of the first reactant is other than H. Suitable first reactants include alcohols (i.e., compounds where Y is H). Alcohol starting materials for the process of the present invention wherein the two R's are different and have the formula (CF₂)_(n) F (i.e., the n of one R is not equal to the n of the other R) can be prepared by known methods using lithium aluminum hydride to reduce the corresponding ketones. Alcohol starting materials for the process of the present invention where one R is (CF₂)_(n) F and the other R is H can be prepared by known methods using lithium aluminum hydride to reduce the corresponding acids. Alcohols where one R is (CF₂)_(n) H and one R is H can be prepared by known methods by the reaction of methanol and tetrafluoroethylene as described in U.S. Pat. No. 4,346,250 and in Chem. Abst. 85:159314g. Alcohols where one R is (CF₂)_(n) Cl and one R is H can be prepared by known methods by the reaction of carbon tetrachloride and tetrafluoroethylene. The carbonate esters of the above alcohols (i.e., Y is COOCHR₂) can be prepared by known methods using 0.5 equivalents of phosgene (alcohol basis) and base. Chloroformate esters of the above alcohols (i.e., Y is COCl) can be prepared by known methods using at least an equimolar amount of phosgene (COCl₂). Fluoroformate esters of the above alcohols (i.e., Y is COF) can be prepared by known methods using at least an equimolar amount of carbonyl fluoride (COF₂). Preferred first reactants include those where Y is H, R is selected from H and (CF₂)_(n) F, and n is an integer from 1 to 4. CF₃ CH₂ OH is a particularly useful first reactant.

The reaction may be run without a catalyst, and CCl₄ is particularly effective as the second reactant where no catalyst is added. Nevertheless, a catalyst may optionally be used for the reaction. Suitable catalysts include compounds selected from the group consisting of SbX₅, AsX₅, TaX₅, BX₃, NbX₅, and PX₅, where each X is independently selected from Cl and F. The oxides of Sb, As, Ta, B, Nb and P, which are converted to fluorides under reaction conditions, may also be used as catalysts. However, conversion of the oxides to fluorides typically produces water, which is preferably avoided.

More generally, in preferred embodiments in which a catalyst is used, especially when CCl₄ is not a reactant, effective catalysts are selected from halides which form solutions with HF that are stronger acids than HF itself. A method of ranking is the acidity scale from Chem. Rev., 1982, 82, 593, which shows some acidity functions, H_(f), of fluoride combinations with HF that are of heightened acidity, including those of SbF₅, AsF₅, TaF₅, BF₃, NbF₅, PF₅. H_(f) for HF is -11.0, while H_(f) for the fluorides with catalytic activity ranges from -22.1 to at least -12.6 on this scale. Other compounds with an H_(f) of less than -11 which can also be used as catalysts are ClSO₃ H, CF₃ SO₃ H, and FSO₃ H.

The molar ratio of HF to the R₂ CHOY reactant typically ranges from about 1:1 to about 50:1, and is preferably within the range of from about 3:1 to 30:1. The molar ratio of the R₂ CHOY reactant to the second reactant (e.g., CCl₄) typically ranges from about 1:2 to 25:1, and is preferably within the range of from about 1:1 to 5:1. The process of the present invention is suitably conducted at a temperature in the range of from about 75° C. to about 250° C., preferably from about 125° C. to about 175° C. The reaction time, in the presence or in the absence of catalyst, is typically from about one minute to about 24 hours, although even higher reaction times can be employed. The reaction variables (e.g., temperature and reactant ratios) can be balanced one against the other such that the reaction can be continued until the yield of fluorinated methyl ether is at least about 25 mol percent (based upon the moles of R₂ CHOY reactant).

One skilled in the art will recognize that water preferably should be avoided in these reactions, and in some instances can react with the second reactant (e.g., COCl₂) under reaction conditions. Nevertheless, limited amounts (e.g., less than about 2 mol %) can generally be tolerated. The reaction is preferably carried out in an essentially anhydrous medium.

The reaction products may be recovered by using conventional separation techniques, such as distillation. A preliminary treatment with water to remove HF, HCl and hydrolyzable by-products facilitates the purification process. Occasionally, as in the case of CF₃ CH₂ OCF₃ and CFCl₃ mixtures, a chemical treatment to remove CFCl₃ from the stable product ether is advantageous. The mixtures may be treated with bases (e.g., NaOH, Na₂ S and Na₂ CO₃) in solution to remove CFCl₃. The fluorinated methyl ethers are stable fluids which are useful as solvents and heat transfer fluids. Low boiling compounds are being considered for use in refrigerant systems.

The chlorine substituent in products of the formula R₂ CHOCF₂ A, where at least one of said R or A group comprises Cl, may, if desired, be replaced with fluorine (e.g., using HF and Cr₂ O₃ catalyst) or hydrogen (e.g., using H₂ and a hydrodechlorination catalyst) or recycled back to the ether synthesis reactor.

The reaction vessels of the process of the present invention should be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride such as Inconel™ nickel alloy and Hastelloy™ nickel alloy.

Pressure is not critical. The pressure may range, for example, from 100 kPa (14.7 psia) to 27.6 mPa (4000 psia), and for many reactor systems is preferably 690 kPa (100 psia) to 6.9 mPa (1000 psia).

Some products and by-products of the process of this invention are considered novel. For example, one can react a first reactant of the formula (CF₃ (CF₂)_(m))₂ CHOH where m is an integer from 0 to 3 with CCl₄ and HF to produce a product containing not only the corresponding trifluoromethylether (CF₃ (CF₂)_(m))₂ CHOCF₃, but also a novel bis-ether of the formula (CF₃ (CF₂)_(m))₂ CHOCF₂ OCH((CF₂)_(m) CF₃)₂. Thus (CF₃)₂ CHOH can be reacted with CCl₄ and HF to produce both (CF₃)₂ CHOCF₃ and (CF₃)₂ CHOCF₂ OCH(CF₃)₂. These novel bis-ethers may be recovered using conventional techniques and used, for example, as chlorine-free solvents or heat transfer fluids.

Practice of the invention will become further apparent from the following nonlimiting Examples.

EXAMPLE 1 2,2,2-Trifluoroethyl Trifluoromethyl Ether CF₃ CH₂ OH+HF+CCl₄ →CF₃ CH₂ OCF₃

Fifty grams (0.50 mol) of CF₃ CH₂ OH, 192 g (1.25 mol) of CCl₄, 280 g (14 mol) of HF, and 7 g (0.1 mol) of BF₃ were charged to a 1.2 liter metal tube and the mixture was agitated at 150° C. and autogeneous pressure for 8 hours. The tube was cooled and 300 mL of water was pumped in. The tube was brought to room temperature and volatiles (108.6 g) were transferred under vacuum to a 1 liter stainless steel cylinder fitted with a needle valve. The contents of the cylinder were held at 25° C. while low boilers were transferred out at 1 atmosphere and distilled from CaCl₂ through a low-temperature still. A 2.5 mL foreshot having a boiling point range of -14° to 2.5° C., largely CF₂ Cl₂, was followed by 62.7 g of product, boiling point range of 2.5° to 15° C. (mainly 8° to 9° C.), then 8 mL with a boiling point range of 15° to 23.5° C., largely CFCl₃. The main product cut was shown by NMR and GC/MS to be 84% CF₃ CH₂ OCF₃ with 6% CF₂ Cl₂ and 10% CFCl₃ also present, so that 2,2,2-trifluoroethyl trifluoromethyl ether was obtained in 63% yield, 52.7 g.

EXAMPLE 2 2,2,2-Trifluoroethyl Trifluoromethyl Ether CF₃ CH₂ OH+HF+CCl₄ →CF₃ CH₂ OCF₃

A mixture of 75 g (0.75 mol) of CF₃ CH₂ OH, 230.7 g (1.5 mol) of CCl₄, 280 g (14 mol) of HF, and 7 g (0.1 mol) of BF₃ were reacted in a metal tube at 100° C. for 8 hours. Volatile crude product isolated as in Example 1 was 3.9 g of a mixture containing mainly CFCl₃ with CF₃ CH₂ OCF₃ and CF₃ CH₂ OCF₂ Cl as minor components. The mixture of liquid products insoluble in water (203.8 g) was dried and on analysis by GC and GC/MS found to contain 2.4 g (2% yield) of CF₃ CH₂ OCF₃, 8.8 g (6% yield) of 2,2,2-trifluoroethyl chlorodifluoromethyl ether (CF₃ CH₂ OCF₂ Cl), and 47.9 g (57%) of bis(2,2,2-trifluoroethyl) carbonate, along with CFCl₃, CCl₄ and some bis(2,2,2-trifluoroethyl) ether. Fractionation afforded a sample boiling point 22° to 23° C. indicated by ¹ H and ¹⁹ F NMR and GC to contain CF₃ CH₂ OCF₂ Cl and CFCl₃. A pure cut, boiling point 116° to 118° C., 40.7 g, was identified as bis(2,2,2-trifluoroethyl) carbonate by GC and ¹ H, ¹⁹ F NMR.

EXAMPLE 3 2,2,2-Trifluoroethyl Trifluoromethyl Ether CF₃ CH₂ OH+HF+CFCl₃ →CF₃ CH₂ OCF₃

A Hastelloy™ nickel alloy tube charged with 75 g (0.75 mol) of trifluoroethanol, 206.1 g (1.50 mol) of CFCl₃, 280 g (14 mol) of HF, and 7 g (0.1 mol) of BF₃ was heated at 150° C. for 8 hours. The tube was cooled to 25° C., 500 g of distilled water was pumped in, the tube was recooled, and volatile products were transferred under vacuum to a 1 liter stainless steel cylinder. The volatiles (203.4 g) were shown by ¹⁹ F NMR analysis to contain 117.6 g (93%) of 2,2,2-trifluoroethyl trifluoromethyl ether, 74.8 g (36% recovery) of CFCl₃, and 10.9 g (6%) of CF₂ Cl₂.

EXAMPLE 4 2,2,2-Trifluoroethyl Trifluoromethyl Ether CF₃ CH₂ OH+HF+CCl₄ →CF₃ CH₂ OCF₃ (No Catalyst)

A 1.2-L metal tube charged with 100.0 g (1.0 mol) of trifluoroethanol, 192.3 g (1.25 mol) of CCl₄, and 280 g (14 mol) of HF was heated at 150° C. for 8 hours, then cooled to 25° C. Addition of 500 g of water, recooling, and transfer of volatile products under vacuum afforded 144.4 g of a low-boiling mixture. The composition in mol % indicated by ¹ H and ¹⁹ F NMR analysis was 62.0% CFCl₃ (85.5 g), 3.2% CF₂ Cl₂ (3.9 g), 0.6% CF₃ CH₂ OCF₂ Cl (1.2 g), 17.7% CF₃ CH₂ OCF₃ (29.9 g), 8.9% CF₃ CH₂ OCH₂ CF₃ (16.2 g), and 7.6% CF₃ CHF (7.8 g).

Water-insoluble liquid products of the reaction weighed 51.8 g. Analysis by GC and by ¹ H and ¹⁹ F NMR showed it to contain 10.5 g of CFCl₃, 0.9 g of CF₃ CH₂ OCF₃, and 39.8 g of (CF₃ CH₂ O)₂ C═O. Total conversions were 18% (30.8 g) CF₃ CH₂ OCF₃, 1% (1.2 g) CF₃ CF₂ OCF₂ Cl, 8% (7.8 g) CF₃ CH₂ F, 35% (39.8 g) (CF₃ CH₂ O)₂ C═O, 12% (16.2 g) CF₃ CH₂ OCH₂ CF₃, 3% (3.9 g) CF₂ Cl₂, and 56% (96.0 g) CFCl₃.

EXAMPLE 5 2,2,2-Trifluoroethyl Trifluoromethyl Ether (CF₃ CH₂ O)₂ C═O+HF+CCl₄ →CF₃ CH₂ OCF₃

A mixture of 90.4 g (0.40 mol) of (CF₃ CH₂ O)₂ C═O, 230.7 g (1.5 mol) of CCl₄, 130 g (6.5 mol) of HF, and 7 g (0.1 mol) of BF₃ was heated in a 1.2 liter vessel at 150° C. for 8 hours. The reaction mixture was cooled to 25° C., 500 mL of water was pressured in, the mass was again cooled and volatiles (198.2 g) were transferred under vacuum to a metal cylinder. Liquid product (56.9 g) was collected as a water-insoluble phase and dried over CaSO₄. Analysis of these products by GC, GC/MS and NMR showed them to contain CF₃ CH₂ OCF₃ (25% conv.) , CF₃ CH₂ OC(O)F (11% conv. ), CFCl₃ (67% conv.), and small amounts of CF₃ CH₂ OCF₂ Cl, CF₃ CH₂ OCF₂ OCH₂ CF₃, CF₃ CH₂ OCOCl, CF₃ CH₂ OCH₂ CF₃, and CF₂ Cl₂.

EXAMPLE 6 2,2,2-Trifluoroethyl Trifluoromethyl Ether CF₃ CH₂ OH+HF+COF₂ →CF₃ CH₂ OCF₃

Reaction of 75 g (0.75 mol) of CF₃ CH₂ OH, 130 g (6.5 mol) of HF, 132 g (2.0 mol) of COF₂, and 7 g (0.1 mol) of BF₃ under pressure at 150° C. for 8 hours, followed by quenching with 500 mL of water gave 70.0 g of volatile products and 3 g of liquid products. Analysis by GC, GC/MS and NMR indicated that a 27% conv. to CF₃ CH₂ OCF₃, 28% conv. to CF₃ CH₂ OC(O)F, 7% conv. to CF₃ CH₂ F, and 3% conv. to (CF₃ CH₂ O)₂ C═O had been attained.

EXAMPLE 7 2,2,2-Trifluoroethyl Trifluoromethyl Ether CF₃ CH₂ OH+HF+COCl₂ →CF₃ CH₂ OCF₃

A 1.3 liter metal tube charged with 35 g (0.35 mol) of CF₃ CH₂ OH, 130 g (6.5 mol) of HF, 71 g (0.72 mol) of COCl₂, and 7 g (0.1 mol) of BF₃ was heated at 150° C. for 10 hours. Water (500 g) was pressured into the cooled tube, and volatiles (23.2 g) were transferred under vacuum to a metal cylinder. Analysis of the volatile product by ¹ H and ¹⁹ F NMR showed that 22.3 g (38%) of CF₃ CH₂ OCF₃ and 0.9 g (3%) of CF₂ CH₂ F were present with traces of CF₃ CH₂ OC(O)Cl and (CF₃ CH₂ O)₂ C═O.

EXAMPLE 8 Trifluoromethyl 2,2,3,3-Trifluoropropyl Ether HCF₂ CF₂ CH₂ OH+HF+CCl₄ →HCF₂ CF₂ CH₂ OCF₃

A 1.2 liter tube charged with 66.0 g (0.50 mol) of HCF₂ CF₂ CH₂ OH, 192 g (1.25 mol) of CCl₄, 250 g (12.5 mol) of HF, and 7 g (0.1 mol) of BF₃ was held at 150° C. for 8 hr. Water (300 mL) was pumped into the cooled reactor, which was recooled to 25° C. The water-insoluble liquid product (63 g) was separated, dried over CaSO₄, and distilled to afford 22.6 g (23%) of trifluoromethyl 2,2,3,3-tetrafluoropropyl ether, boiling point 45.9° to 46.3° C., identified by GC, GC/MS, IR, and NMR. GC indicated that the crude product contained 41.5 g (41% conv.) of HCF₂ CF₂ CH₂ OCF₃.

EXAMPLE 9 Trifluoromethyl 2-Chloro-2,2-difluoroethyl Ether ClCF₂ CH₂ OH+HF+CCl₄ →ClCF₂ CH₂ OCF₃

A reaction of 58.3 g (0.50 mol) of ClCF₂ CH₂ OH, 192 g (1.25 mol) of CCl₄, 280 g (14 mol) of HF, and 7 g (0.1 mol) of BF₃ was carried out as described for Example 8. The liquid product (18.7 g) was determined by GC and GC/MS to contain 2.4 g (3%) of ClCF₂ CH₂ OCF₃.

EXAMPLE 10 2,2,2-Trifluoroethyl Trifluoromethyl Ether CF₃ CH₂ OH+HF+CCl₄ →CF₃ CH₂ OCF₃

A 1.3 liter Hastelloy™ nickel alloy tube charged with 30 g (0.10 mol) of SbCl₅ and 280 g (14 mol) of HF was agitated at 60° C. for 1 hr, then cooled. A mixture of 100 g (1.0 mol) of CF₃ CH₂ OH and 192.3 g (1.25 mol) of CCl₄ was pressured in, and the tube was heated at 100° C. for 8 hours. The reactor was cooled, 500 g of water was pumped in, the reactor was cooled again to 30° C., and then volatile products (115 g) were transferred under vacuum to a metal cylinder. Liquid product (54 g) was collected separately. Analyses by GC and NMR showed the presence of 15.5 g (9%) of CF₃ CH₂ OCF₃, large amounts of (CF₃ CH₂ O)₂ C═O and CFCl₃, with small amounts of CF₃ CH₂ OCF₂ Cl, CF.sub. 2 Cl₂, and CF₃ CH₂ OCH₂ CF₃ also present.

EXAMPLE 11 2,2,2-Trifluoroethyl Trifluoromethyl Ether B₂ O₃ as Catalyst

A metal tube charged with 3.5 g (0.05 mol) of B₂ O₃, 100.0 g (1.0 mol) of CF₃ CH₂ OH, 192.3 g (1.25 mol) of CCl₄, and 280 g (14 mol) of HF was agitated for 10 hr at 150° C. Water, 500 mL, was added to the tube, and 120.1 g of volatile product was transferred out after cooling to 30° C. Analysis by GC and ¹ H and ¹⁹ F NMR showed the presence of 99.7 g (59%) of CF₃ CH₂ OCF₃ along with CFCCl₃ and very small amounts of other products.

EXAMPLE 12 2,2,2-Trifluoroethyl Trifluoromethyl Ether TaF₅ as Catalyst

A 100 mL Inconel™ nickel alloy tube containing a magnetic stirrer, an internal thermocouple and equipped with a condenser, back-pressure regulator, and an on-line analytical system was charged with TaF₅ (8.0 g, 0.03 mol). The reactor was then cooled, evacuated and charged with CF₃ CH₂ OH (8.0 g, 0.08 mol), CCl₄ (24 g, 0.16 mol) and anhydrous HF (5 mL, 0.25 mol). The reactor was then pressurized with nitrogen (200 psig, 1480 kPa) and gradually heated to 150° C. with stirring. The back-pressure regulator was set at 500 psig (3550 kPa). After 2 hours at 150° C., the reaction was stopped and the reactor contents analyzed by GC. The results in area % were as follows:, CF₃ CH₂ OCF₃ (54.4%), (CF₃ CH₂ O)₂ C═O (0.3%), CCl₄ (0.1%), CCl₃ F (2.5%), CCl₂ F₂ (19.8%), CClF₃ (1.2%), CHCl₂ CF₃ (0.3%), CH₂ ClCF₃ (0.9%) and CH₂ FCF₃ (20.0% ).

EXAMPLE 13 2,2,2-Trifluoroethyl Trifluoromethyl Ether Purification

A 105 g portion of the reaction product from the reaction of CF₃ CH₂ OH, CCl₄ and HF containing 85% CF₃ CH₂ OCF₃ and 15% CFCl₃ and trace impurities was purified according to the herein described procedure. The reaction product was treated with 120 g Na₂ S.9H₂ O dissolved in 500 mL of dimethyl formamide at 100° C. for 10 hours. After cooling to room temperature, the solution was passed successively through 10% aqueous potassium hydroxide, 10% sulfuric acid and finally through a tube containing anhydrous calcium sulfate. The purified product was found by GC analysis to be essentially pure CF₃ CH₂ OCF₃ and trace impurities. ¹ H and ¹⁹ F NMR showed the purified product to contain CF₃ CH₂ OCF₃, <1% CF₃ CH₂ F and trace amounts of CF₂ Cl₂. This purification was necessary because of the difficulty in separating CFCl₃ from CF₃ CH₂ OCF₃ by distillation.

EXAMPLE 14 (CF₃)₂ CHOH+HF+CCl₄ →(CF₃)₂ CHOCF₃ +(CF₃)₂ CHOCF₂ Cl+(CF₃)₂ CHOCFCl₂ +(CF₃)₂ CHOCF₂ OCH(CF₃)₂

A 1.3 liter Hastelloy™ nickel alloy tube charged with 168 g (1.0 mol) of hexafluoroisopropanol, 192.3 g (1.25 mol) of CCl₄, 280 g (14 mol) of HF, and 10 g of BF₃ was heated at 150° C. for 10 hours. The tube was then cooled to 25° C., 500 g of water was pumped in, and the tube was cooled again. Volatile products (150.2 g) transferred under vacuum were a mixture indicated by GC to contain 11.4 g of CF₂ Cl₂, 2.7 g of (CF₃)₂ CHOCF₃, 48.7 g of CFCl₃, 79.5 g of (CF₃)₂ CHOCF₂ Cl, 2.7 g of (CF₃)₂ CHOCFCl₂, and 5.3 g of (CF₃)₂ CHOCF₂ OCH(CF₃)₂. Water-insoluble liquid product (106.3 g) was shown by GC and GC/MS analysis to contain 0.5 g of CF₂ Cl₂, 0.6 g of (CF₃)₂ CHOCF₃, 10.0 g of CFCl₃, 63.6 g of (CF₃)₂ CHOCF₂ Cl, 4.5 g of (CF₃)₂ CHOCFCl₂, and 27.1 g of (CF₃)₂ CHOCF₂ OCH(CF₃)₂. Combining, the totals obtained were 3.3 g (1.4% yield) of (CF₃)₂ CHOCF₃, 143.1 g (57%) of (CF₃)₂ CHOCF₂ Cl, 7.2 g (2.7%) of (CF₃)₂ CHOCFCl₂, and 32.4 g (17%) of (CF₃)₂ CHOCF₂ OCH (CF₃)₂.

Fractionation of the combined products afforded 23.2 g of a mixture, boiling point up to 39.5° C., shown by ¹ H and ¹⁹ F NMR and GC to contain mainly CFCl₃ and (CF₃)₂ CHOCF₂ Cl along with a small amount of trifluoromethyl 1,1,1,3,3,3-hexafluoro-2-propyl ether. There was then distilled 120.1 g, boiling point 40° to 45° C., identified by GC and NMR as chlorodifluoromethyl 1,1,1,3,3,3-hexafluoro-2-propyl ether. Next came 2.7 g, boiling point 75° to 79° C., of dichlorofluoromethyl 1,1,1,3,3,3-hexafluoro-2-propyl ether, identified by GC and NMR. Finally, there was obtained 24.4 g of 2,6-bis(trifluoromethyl)1,1,1,4,4,7,7,7-octafluoro-3,5-dioxaheptane, ((CF₃)₂ CHOCF₂ OCH(CF₃)₂), boiling point 89° to 94° C. identified by GC and NMR analyses. NMR and mass spectroscopic (MS) analyses of (CF₃)₂ CHOCF₂ OCH(CF₃)₂ are as follows: ¹ H-NMR (CDCl₃) δ 4.78 (septet, J_(HF), 5.4 Hz, OCH(CF₃)₂); ¹⁹ F-NMR (CDCl₃) φ-60.9 (m, 2F, OCF₂ O), -74.3 (m, 12F, CF₃). MS, m/e 364.966156 (M⁺ -F; mass meas. C₇ H₂ F₁₃ O₂), 314.9808 (M⁺ -CF₃), 216.983002 (mass meas. (CF₃)₂ CHOCF₂ ⁺), 150.9758 (CF₃ CHCF₃ ⁺).

EXAMPLE 15 (CF₃)₂ CHOH+HF+CCl₄ →(CF₃)₂ CHOCF₃ +(CF₃)₂ CHOCF₂ Cl+(CF₃)₂ CHOCFCl₂ +(CF₃)₂ CHOCF₂ OCH(CF₃)₂

A mixture of 143 g (0.85 mol) of (CF₃)₂ CHOH, 169 g (1.1 mol) of CCl₄, 240 g (12 mol) of HF, and 10 g of BF₃ was heated in a 1.3 liter tube for 8 hours at 150° C., then for 4 hours at 180° C. Water (500 g) was added to the cooled mixture, and volatiles (163 g) and water-insoluble liquid (75.3 g) were isolated as before. Analyses by GC and NMR showed the product to contain 28.1 g of CF₂ Cl₂, 9.0 g (4.5% conv. to) of (CF₃)₂ CHOCF₃, 40.0 g of CFCl₃, 141.0 g (66%) of (CF₃)₂ CHOCF₂ Cl, 1.7 g (1%) of (CF₃)₂ CHOCFCl₂, and 18.5 g (11%) of (CF₃)₂ CHOCF₂ OCH(CF₃)₂.

Reaction at higher temperature than the Example 14 led to a higher conversion to the trifluoromethyl ether.

EXAMPLE 16 Trifluoromethyl Methyl Ether CH₃ OH+HF+CCl₄ →CH₃ OCF₃ (No Catalyst)

A 1L Hastelloy™ nickel alloy tube charged with 32.0 g (1.0 mol) of methanol, 153.8 g (1.0 mol) of CCl₄, and 120 g (6.0 mol) of HF was heated at 100° C. for 10 hours, then cooled to 25° C. Addition of 500 g of water, recooling, and transfer of volatile products under vacuum afforded 5.3 g of a low-boiling mixture. Analysis by GC/MS showed the product mixture to contain, CH₃ F, CH₃ Cl, CH₃ OCH₃, CH₃ OCF₃, CFCl₃ and CCl₄. 

What is claimed is:
 1. A product comprising a bis-ether of the formula (CF₃ (CF₂)_(m))₂ CHOCF₂ OCH((CF₂)_(m) CF₃)₂ wherein m is an integer from 0 to 3, produced by a process comprising reacting a first reactant of the formula (CF₃ (CF₂)_(m))₂ CHOH with CCl₄ and HF to produce (CF₃ (CF₂)_(m))₂ CHOCF₃ and said bis-ether.
 2. A bis-ether compound of the formula (CF₃ (CF₂)_(m))₂ CHOCF₂ OCH((CF₂)_(m) CF₃)₂, wherein m is an integer from 0 to
 3. 3. The bis-ether compound in accordance with claim 2 having the formula (CF₃)₂ CHOCF₂ OCH(CF₃)₂.
 4. A product comprising a bis-ether of the formula (CF₃ (CF₂)_(m))₂ CHOCF₂ OCH((CF₂)_(m) CF₃)₂, wherein m is an integer from 0 to 3, produced a process comprising reacting a first reactant of the formula (CF₃ (CF₂)_(m))₂ CHOH, with CCl₄ and HF in the presence of a catalyst selected from the group consisting of SbX₅, AsX₅, TaX₅, BX₃, NbX₅ and PX₅, wherein each X is independently selected from Cl and F, to produce (CF₃ (CF₂)_(m))₂ COCF₃ and said bis-ether. 